+

WO1998044080A1 - Aerosol hard surface cleaner with enhanced soil removal - Google Patents

Aerosol hard surface cleaner with enhanced soil removal Download PDF

Info

Publication number
WO1998044080A1
WO1998044080A1 PCT/US1998/005224 US9805224W WO9844080A1 WO 1998044080 A1 WO1998044080 A1 WO 1998044080A1 US 9805224 W US9805224 W US 9805224W WO 9844080 A1 WO9844080 A1 WO 9844080A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
surfactant
edta
die
effective amount
Prior art date
Application number
PCT/US1998/005224
Other languages
French (fr)
Inventor
Maria Ochomogo
Teressa Brandtjen
Scott C. Mills
Jennifer C. Julian
Michael H. Robbins
Original Assignee
The Clorox Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Clorox Company filed Critical The Clorox Company
Priority to CA002291223A priority Critical patent/CA2291223A1/en
Priority to EP98910456A priority patent/EP1015535A1/en
Priority to AU64695/98A priority patent/AU760853B2/en
Publication of WO1998044080A1 publication Critical patent/WO1998044080A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0043—For use with aerosol devices
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/755—Sulfoxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/79—Phosphine oxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Definitions

  • the present invention relates generally to aerosol hard surface cleaners that are especially effective on bathroom soils, such as soap scum and particularly to a dispensable composition that forms a foam on the surface of stained and soiled surfaces which readily collapses to deliver the cleaning formulation.
  • a number of hard surface cleaners have been specially formulated to target bathroom soils. These include products containing liquid hypochlorite for combating mildew and fungus; products with quaternary ammonium compounds as bacteriostats; and acidic cleaners, such as those containing phosphoric or other strong mineral acids. These cleaners will typically include buffers, dyes, fragrances, and die like in order to provide performance and/ or aesthetic enhancements.
  • Gipp U.S. 4,595,527, discloses a laundry prespotter consisting essentially of at least 5% nonionic surfactants and chelating agents, including ammonium EDTA, but which is substantially solvent-free.
  • Murtaugh, U.S. 4,029,607 discloses the use of ammonium EDTA in a drain opener
  • Bolan U.S. 4,207.215
  • a thixotropic gel for tile cleaning.
  • Neither of these two references discloses, teaches or suggests die presence of a solvent, nor discloses, teaches or suggests the formulation of an aerosol bathroom cleaner with enhanced soil removal.
  • Graubart et al., U.S. 5,454,984 discloses a cleaning composition comprising quaternary ammonium compounds, tetrasodium EDTA, a mixture of surfactants, and a glycol ether.
  • the present invention is directed to a foam forming aerosol cleaning composition that is particularly suited for cleaning hard surfaces.
  • the invention is based in part on the discovery mat the aerosol formulations of a hard-surface cleaner mat includes a chelating agent comprising potassium EDTA and/or ammonium EDTA are superior in applying the cleaner over a surface area without adversely affecting the cleaning abilities of the cleaner.
  • the invention is directed to a dispensable composition for cleaning hard surfaces that includes:
  • a chelating agent selected from me group consisting of tetrapotassium ethylenediamine - tetraacetate (potassium EDTA), tetraammonium ethylenediamine-tetraacetate (ammonium EDTA) and mixtures thereof, said chelating agent present in an amount effective to enhance soil removal in said composition;
  • the invention is directed to a device, for dispensing a composition for cleaning hard surfaces, which includes, a closed container containing the above referenced cleaning composition and nozzle means for releasing said composition towards a soiled surface.
  • the invention provides an aerosol formulation comprising an improved, all purpose cleaner especially adapted for the complete and speedy removal of soap scum and other bathroom soils from a hard surface.
  • the cleaner is intended to clean hard surfaces by aerosol application of a metered discrete amount of me cleaner by a dispenser onto me surface to be cleaned and then wiping the surface, thus removing the soil and die cleaner, wim or without the need for rinsing with water. Foaming action facilitates dispersal of the active components.
  • the typical bathroom surface is a shower stall, both the glass doors, as well as me vertical wall surfaces (typically made of tile, or composite materials), sinks and glass.
  • the aerosol formulation comprises a cleaning composition mat is mixed wim a propellant.
  • the cleaning composition or cleaner itself prior to being mixed wim me propellant is preferably a single phase, clear, isotropic solution, having a viscosity generally less than about 100 Centipoise ("cps").
  • the cleaning composition itself has the following ingredients:
  • a chelating agent selected from ammonium ethylenediamine - tetraaecetate (ammonia EDTA), tetrapotassium emylenediamine - tetraacetate (potassium EDTA), or mixtures thereof, said chelating agent present in an amount effective to enhance soil, especially soap scum, removal in said cleaner; and (d) die remainder, water.
  • adjuncts in small amounts such as buffers, fragrance, dye and die like can be included to provide desirable attributes of such adjuncts.
  • the solvent is a water soluble or dispersible organic solvent having a vapor pressure of at least 0.001 mm Hg at 25 "C. It is preferably selected from C ⁇ alkanol, C ⁇ diols, C 3-24 aikylene glycoi ethers, and mLxmres thereof.
  • the alkanol can be selected from methanol, ethanol, n-propanol. isopropanol. butanol, pentanoi, hexanoi, dieir various positional isomers, and mLxmres of d e foregoing. It may also be possible to utilize in addition to, or in place of, said alkanols, the diols such as memylene, ethylene, propylene and butylene glycols, and mixtures thereof.
  • the aikylene glycoi ether solvents can include emylene glycoi monobutyl ether, emylene glycoi monopropyl edier, propylene glycoi n-propyl etfier, propylene glycoi monobutyl ether, diemylene glycoi n-butyl ether, dipropylene glycoi memyl ether, and mLxmres mereof.
  • Preferred glycoi ediers are emylene glycoi monobutyl ether, also known as butoxyedianol, sold as butyl Cellosolve by Union Carbide, and also sold by Dow Chemical Co., 2-(2-butoxyethoxy) ethanol, sold as butyl Carbitol, also by Union Carbide, and propylene glycoi n-propyl ether, available from a variety of sources.
  • Anodier preferred aikylene glycoi ether is propylene glycoi, t-butyl ether, which is commercially sold as Arcosolve PTB, by Arco Chemical Co.
  • the n-butyl edier of propylene glycoi is also preferred. Odier suppliers of preferred solvents include Union Carbide.
  • d e amounts and ratios of such solvents used are important to determine the optimum cleaning and streak/film performances of the inventive cleaner. It is preferred co limit the total amount of solvent to no more than 50% , more preferably no more man 25 , and most preferably, no more man 15 % . of the cleaner. A preferred range is about 1-15 % .
  • These amounts of solvents are generally referred to as dispersion-effective or solubilizing effective amounts, since the other components, such as surfactants. are materials which are assisted into solution by the solvents. The solvents are also important as clearing materials en their own. helping to lcosen and solubilize greasy soils for easy removal from the surface cleaned. 2.
  • the surfactant is an anicnic, nonionic. amphcteric surfactant, or mLxmres thereof.
  • a quaternary ammonium surfactant can be added.
  • the anionic surfactant is, for example, a linear or branched C_.; 4 alkylbenzene sulfonate, alkane sulfo ⁇ ate. alkyl sulfate. or generally, a sulfated or sulfonated ., 4 surfactant.
  • Witconate NAS for example, is a 1-octane-sulfonate. from Witco Chemical Company. Pilot L-45. a C 1! 5 alkylbenzene sulfonate (which are referred to as "LAS"), from Pilot Chemical Co.
  • Biosoft S100 and S130 non-neutralized linear alkylbenzene sulfonic acid, which is referred to as "HLAS" and S40 from Stepan Company; sodium dodecyl sulfate and sodium lauryl sulfate.
  • HLAS non-neutralized linear alkylbenzene sulfonic acid
  • S40 from Stepan Company
  • sodium dodecyl sulfate and sodium lauryl sulfate sodium dodecyl sulfate and sodium lauryl sulfate.
  • acidic surfactants having a higher actives level may be desirable due to cost-effectiveness.
  • the nonionic surfactants are selected from alkoxvlated alcohols, alkoxylated phenol ethers, and odier surfactants often referred to as semi-polar nonionics, such as the trialkyl amine oxides.
  • the alkoxylated phenol ethers include octyl- and nonylphenol ediers, with varying degrees of alkoxylation, such as 1-10 moles of ethylene oxide per mole of phenol.
  • the alkyl group can vary from C_. lfi , although octyl- and nonyl chain lengths are readily available.
  • Triton such as Triton N-57, N-101, N-lll, X-45, X-100, X-102, and from Mazer Chemicals under the trademark Macol, from GAF Corporation under d e trademark Igepal. from Texaco Chemical Company under the trademark Surfonic.
  • Tne alkoxylated alcohols include ethoxylated. and ethoxylated and propoxylated C_. ;6 alcohols, with about 2-10 moles of ethylene oxide, or 1-10 and 1-10 moles of ethylene and propylene oxide per mole of alcohol, respectively.
  • Exemplary surfactants are available from Shell Chemical under the trademarks Neodol and Alfonic and Huntsman.
  • the semi-polar amine oxides are aiso preferred, although, for the invention, a mixture of nonionic and amine oxide surfactants can also be used.
  • the amine oxides referred to as mono-long chain, di-short chain, trialkyl amine oxides, have ⁇ e general configuration:
  • R 1 is C ⁇ ., alkyl, and R : and R 3 are both C 14 alkyl, or C hydroxyalkyl, altfiough R : and R 3 do not have to be equal.
  • These amine oxides can also be ethoxylated or propoxylated.
  • the preferred amine oxide is lauryl amine oxide.
  • the commercial sources for such amine oxides are Barlox 10, 12, 14 and 16 from Lonza Chemical Company. Varox by Witco and Ammonyx by Stepan Co.
  • a further preferred semi-polar nonionic surfactant is alkylamidoall ylenedialkylamine oxide. Its structure is shown below:
  • R 1 is C 5 . :o alkyl
  • R- and R 3 are C alkyl
  • n is 1-5. preferably 3.
  • p is i- ⁇ . preferably 2-3.
  • the surfactant could be ethoxylated (1-10 moles of EO/mole) or propoxylated (1-10 moles of PO/mole). This surfactant is available from various sources, including from Lonza Chemical Company, as a cccoamidopropyldimethyl amine oxide, sold under the brand name Bariox C.
  • semi-polar surfactants include phcsphine oxides and sulfoxides.
  • amphoteric surfactant is typically an alk lbetaine or a sulfobetaine.
  • alk lbetaine or a sulfobetaine.
  • One group of preferred amphoterics are alkyiamidoaikyidialkylbetaines. Tnese have the structure:
  • R 1 is C_. o alkyl, R : and R 3 are bom C alkyl. although R : and R 3 do not have to be equal, and m can be 1-5, preferably 3, and n can be 1-5, preferably 1.
  • alkvlbetaines can also be ethoxylated or propoxylated.
  • the preferred alkylbetaine is a cocoamidopropyldimethyl betaine called Lonzaine CO, available from Lonza Chemical Co.
  • Other vendors are Henkel KGaA, which provides Velvetex AB, and Witco Chemical Co. , which offers Rewoteric AMB-15, borJa of which products are cocobetaines.
  • the amounts of surfactants present are to be somewhat minimized, for purposes of cost-savings and to generally restrict the dissolved actives which could contribute to leaving behind residues when die aerosol is applied to a surface.
  • die amounts added are generallv about 0.001-10% , more preferably 0.002-3.00% surfactant. These are generally considered to be cleaning-effective amounts. If a mixture of anionic and nonionic or amphoteric surfactants is used, die ratio of the anionic surfactant to the nonionic or amphoteric su ⁇ actant is about 20:1 to 1:20. more preferably about 10: 1 to 1: 10. b. Quaternary .Ammonium Surfactant
  • the invention may further optionally include a cationic surfactant, specifically, a quaternary ammonium surfactant.
  • a cationic surfactant specifically, a quaternary ammonium surfactant.
  • bo gram positive e.g. , S tap hv loco ecus s_ .
  • gram negative e.g.. Escherischia coif* microorganisms. Tnus, the quaternary ammonium surfactant, or compounds. are incorporated for bacteriostatic/disinfectant purposes and should be present in amounts effective for such purposes.
  • the quaternary ammonium compounds are selected from mono-long-chain, tri-short-chain, tetraalkyl ammonium compounds, di-long-chain. di-short-chain tetraalkyl ammonium compounds, trialkyl, mono-benzyl ammonium compounds, and mLxmres thereof.
  • long chain is meant about alkyl.
  • short chain is meant C 1-3 alkyl, preferably C I-3 .
  • Preferred materials include Stepan series, such as d e BTC 2125 series which comprises di-C_ 4 tetraalkyl ammonium chloride, Barquat and Bardac series, such as Bardac MB 2050, from Lonza Chemical. Typical amounts of die quaternary ammonium compound range from preferably about 0-5 % , more preferably about 0.001-2%. 3. Chelating Agent
  • the chelating agent comprises tetraammonium ethylenediamine tetraacetate (referred to as “ammonium EDTA”), tetrapotassium ethylene diaminetetraacetate (referred to as “potassium EDTA”), or mLxmres thereof.
  • ammonium EDTA tetraammonium ethylenediamine tetraacetate
  • potassium EDTA tetrapotassium ethylene diaminetetraacetate
  • mLxmres thereof mLxmres thereof.
  • the chelating agent is a critical part of die invention. Its use, in place of the standard chelating agent, tetrasodium EDTA, results in not only a surprisingly complete removal of various soils, including badiroom soap scum soils, but an unexpectedly rapid removal as well.
  • the potassium EDTA can favorably be prepared by taking the acid form of EDTA and neutralizing it with KOH in a stoichiometric quantity.
  • KOH solution for example, to 50g of the acid form of EDTA and 47g deioniz ⁇ d water, 76g of KOH solution (45 %) can be siowly added, resulting in a 46% K»EDTA solution.
  • the acid form of EDTA can be obtained from Hampshire Chemicals and Aldrich Chemicals.
  • me neutralization of the acid form of EDTA it is preferred to use an excess of alkali.
  • the level of KOH can vary from a stoichiometric quantity to from about a 0 to 5 % excess.
  • the amount of ammonium EDTA and or potassium EDTA added should be in the range of 0.01-25 %, more preferably 0.01-10% , by weight of the cleaner. Moreover, a discrete quantity of a co-chelant, such as tetrasodium EDTA may be added, in an amount ranging from about 1-5% . 4. Water and Miscellaneous
  • die cleaner is an aqueous cleaner with relatively low levels of actives
  • die principal ingredient is water, which should be present at a level of at least about 50% , more preferably at least about 80%, and most preferably, at least about 90%. Deionized water is preferred.
  • adjuncts can be added for improving cleaning performance or aesthetic qualities of the cleaner.
  • buffers could be added to maintain constant pH (which for the invention is between about 7-14, more preferably between about 8-13).
  • These buffers include NaOH. KOH. Na : C0 3 , K ; C0 3 , as alkaline buffers, and phosphoric, hydrochloric. sulfuric acids as acidic buffers, and others.
  • KOH is a prererred buffer since, in die invention, one way of obtaining potassium EDTA is to take the acidic EDTA acid and neutralize :: w. ⁇ an appropriate, st.ichiometric amount of KOH.
  • Builders such as phosphates, silicates, and again, carbonates, may be desirable.
  • soiu iiizing materials such as hydrctropes, e.g.. cumene. toluene and xylene sulfonates. may also be desirable.
  • Adjuncts for cleaning include additional surfactants, such as those described in Kirk-Othmer. Encyclopedia of Chemical Technology, 3rd Ed.. Volume 22, pp. 332-432 (Marcel-Dekker, 1983), and McCutcheon's Soaps and Detergents (N. Arner. 1984), which are incorporated herein by reference.
  • Aesthetic adjuncts include fragrances, such as diose available from Givaudan, IFF, Quest, Sozio, Firmenich, Dragoco and others, and dyes and pigments which can be solubiliz ⁇ d or suspended in the formulation, such as diaminoandiraquinones.
  • Water-insoluble solvents may sometimes be desirable as added grease or oily soil cutting agents. These types of solvents include tertiary alcohols. hydrocarbons (alkanes), pine-oil. d-limonene and od er terpenes and terpene derivatives, and benzyl alcohols.
  • Thickeners such as calcium carbonate, sodium bicarbonate, aluminum oxide, and polymers, such as poly aery late, starch, xanthan gum, alginates, guar gum, cellulose, and die like, may be desired additives.
  • the use of some of these thickeners (CaCO 3 or NaHCO 3 ) is to be distinguished from their potential use as builders, generally by particle size or amount used. 5.
  • the cleaning composition is delivered in die form of an aerosol.
  • die cleaning composition is delivered via a gaseous propellant.
  • the propellant comprises, for example, a hydrocarbon, of from 1 to 10 carbon atoms, such as methane, ediane. n- propane, n-butane. isobutane, n-pentane. isopentane. and mLxmres diereof.
  • the propellant may also be selected form halogenated hydrocarbons including, for example, fluorocarbons. chlorocarbons. chlorofluorccarbons. and mLxmres thereof. Examples of odier suitable propeilants are founded in P. A. Sanders Handbook of Aerosol Technology: (Van Nostrand Reinhold Co.)(l9" " 9) 2nd Ed. , Pgs. 348-353 and 364-367, which are incorporated herein.
  • a liquified gas propellant mLxrure comprising about S5% isobutane and 15% propane is preferred because it provides sufficient pressure to expel the cleaning composition from the container and provides good control over the nature of the spray upon discharge of d e aerosol formulation.
  • the propeilants comprises about 3 % to 30%, more preferably about 3 % to 8% , and most preferably about 3 % to 6% of d e aerosol formulation.
  • the aerosol formulation is preferably stored in and dispensed from a pressurized can that is equipped with a nozzle so that an aerosol of die formulation can be readily sprayed onto a surface to create a relatively uniform layer of foam.
  • a preferred nozzle is a toggle valve model ST-76 with an orifice size of 0.016 in. (0.4 mm) that is manufactured by Seaquist Perfect Dispensing, Cary, Illinois. Dispensers are known in the art and are described, for example, in U.S. Patents 4,780,100, 4,652,389, and 3,541,581 which are incorporated herein.
  • a preferred range is about 40 to 58 lbs./hr, more preferably 40 to 50 lbs Jin 2 , and most preferably 40 to 47 lbs Jin 2 at 70° F (21 °C).
  • the corrosion inhibitor is used to prevent or at least reduce die rate of corrosion of a metallic dispenser. Quaternary ammonium surfactants, if present, can cause corrosion.
  • Preferred corrosion inhibitors include, for example: amine neutralized alkyl acid phosphates, amine neutralized alkyl acid phosphates and nitroalkanes. amine neutralized alkyl acid phosphates and volatile amines, diethanoiamides and nitroalkanes.
  • the corrosion inhibitor preferably comprises about 0.1 % to 1 % . more preferably about 0.1 % to 0.8 % . and most preferably about 0.35 % of die aerosol formulation.
  • the pH of the aerosol formulation is greater than 9.5.
  • inventive aerosol formulations were compared with two commercial bathroom aerosol cleaners, namely. Dow Bathroom Cleaner (Dow Brands) and Lysol Basin Tub & Tile Cleaner (Reckitt & Colman).
  • Table 1 sets forth the non-propellant active components (including corrosium inhibitor) of the two inventive cleaning compositions, one employing potassium EDTA as the chelating agent and die odier employing ammonium EDTA.
  • This laboratory soil simulates aged soap scum and was prepared by making a calcium stearate suspension (ethanol. calcium stearate and water). This soap scum soil was men sprayed onto black ceramic tiles which were baked at 165 ' -170 " C for one hour, then cooled.
  • This example employed tiles prepared by die method described in Protocol ⁇ to which 2 grams of the aerosol compositions were applied to each tile. After the foam had dissipated, which typically occurred in about 45 seconds, die tile was wiped wid a sponge. The tile was visually graded by a panel of expert graders on a 1 to 10 scale, where 1 indicates no soil removal, while 10 indicates complete removal. The observed results are averaged and subject to error analysis using Fisher's least significant difference ("LSD”), wiu a confidence level of 95%. The results are set form in Table 2. As is apparent, the inventive aerosol formulations were superior to die comparative aerosol cleansers.
  • Example 2 Bathroom Soil Removal Test
  • the reader/scrubber measures % soil removal by calibrating with a clean tile, which would establish 100% clean, versus a completely soiled tile, which would establish a zero % clean.
  • Each soiled tile cleaned by the scrubber is measured during die cleaning by die reader to establish the differences in shading between die initially completely soiled panel and die completely cleaned one. The number of cycles to remove 90% of die badiroom soil were measured.
  • Tiles coated with bathroom soil (Protocol I) were used. 15 grams of me aerosol compositions were applied to a previously wetted sponge on die scrubber. The results are depicted in Table 2. These scores are again within die 95% confidence level.
  • the inventive aerosol formulations clearly and unambiguously outperformed the aerosol commercial cleaners.
  • dies prepared by Protocol II were each coated with 15 grams of an aerosol composition and men tested with the reader/scrubber described in Example 2. The number of cycles to remove 90% of die soap scum were measured. The results are depicted in Table 2. These scores are again within the 95% confidence level.
  • the inventive aerosol formulations again clearly and unambiguously outperformed die commercial aerosol cleaners.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

An aerosol cleaning composition for hard surfaces is provided. The dispensable includes: (a) an anionic, nonionic, amphoteric surfactant, and mixtures thereof with optionally, a quaternary ammonium surfactant, the total amount of said surfactant being present in a cleaning effective amount; (b) at least one water-soluble or dispersible organic solvent having a vapor pressure of at least 0.001 mm Hg at 25 °C, said at least one organic solvent present in a solubilizing - or dispersion - effective amount; (c) a chelating agent selected from the group consisting of tetrapotassium ethylenediamine-tetraacetate (potassium EDTA), tetraammonium ethylenediamine-tetraacetate (ammonium EDTA) and mixtures thereof, said chelating agent present in an amount effective to enhance soil removal in said composition; (d) an effective amount of a propellant; and (e) the remainder, water. The forming action of the aerosol composition facilitates the dispersement of the cleaning components.

Description

AEROSOL HARD SURFACE CLEANER WITH ENHANCED SOIL REMOVAL
Inventors: Maria Ochomogo, Teressa Brandtjen, Scott C. Mills, Jennifer C. Julian and Michael H. Robbins.
The present application is a continuation in part application of U.S. Patent Applications Serial No. 08/632,041 filed April 12, 1996 and 08/731,653, filed on October 17, 1996.
Fieid of the Invention The present invention relates generally to aerosol hard surface cleaners that are especially effective on bathroom soils, such as soap scum and particularly to a dispensable composition that forms a foam on the surface of stained and soiled surfaces which readily collapses to deliver the cleaning formulation.
Background of the Invention A number of hard surface cleaners have been specially formulated to target bathroom soils. These include products containing liquid hypochlorite for combating mildew and fungus; products with quaternary ammonium compounds as bacteriostats; and acidic cleaners, such as those containing phosphoric or other strong mineral acids. These cleaners will typically include buffers, dyes, fragrances, and die like in order to provide performance and/ or aesthetic enhancements. Gipp, U.S. 4,595,527, discloses a laundry prespotter consisting essentially of at least 5% nonionic surfactants and chelating agents, including ammonium EDTA, but which is substantially solvent-free.
Murtaugh, U.S. 4,029,607, discloses the use of ammonium EDTA in a drain opener, while Bolan, U.S. 4,207.215, discloses the use of ammonium EDTA in a thixotropic gel for tile cleaning. Neither of these two references, however, discloses, teaches or suggests die presence of a solvent, nor discloses, teaches or suggests the formulation of an aerosol bathroom cleaner with enhanced soil removal. Graubart et al., U.S. 5,454,984, discloses a cleaning composition comprising quaternary ammonium compounds, tetrasodium EDTA, a mixture of surfactants, and a glycol ether. However, the reference fails to teach, disclose or suggest the use of either potassium or ammonium EDTA as a chelating agent. Garabedian et al. , U.S. Patents 5,252,245, 5,437,807 and 5,468.423, and Choy et al., U.S. Patent Application Serial No. 08/410,470. filed March 24. 1995, all of common assignment herewith, disclose improved glass and surface cleaners which combine either amphoteric or nonionic surfactants with solvents and effective buffers to provide excellent streaking/filming characteristics on glass and odier smooth, glossy surfaces.
Co-pending application Serial No. filed February 27,
1996, a continuation of Serial No. 08/507,543, filed July 26. 1995, now abandoned, of Zhou et al., entitled "Antimicrobial Hard Surface Cleaner, " of common assignment, discloses and claims an antimicrobial hard surface cleaner which includes amine oxide, quaternary ammonium compound and tetrasodium EDTA, in which a critical amine oxide: EDTA ratio results in enhanced non-streaking and non-filming performance.
Co-pending application Serial No. 08/605,822, filed February 23, 1996, of Choy et al., entitled "Composition and Apparatus for Surface Cleaning, " of common assignment, discloses and claims a hard surface cleaner which uses a dual chamber delivery system, one chamber containing an oxidant solution and the other, a combination of chelating agents and surfactants.
However, none of the art discloses, teaches or suggests the use of tetrapotassium EDTA and/or tetraammonium EDTA as an effective chelating agent which additionally surprisingly enhances uhe soil removing, especially soap scum-removing, ability of the liquid, one phase cleaners formulated therewith. Additionally, none of the art discloses, teaches or suggests an aerosol formulation of these cleaning compositions.
Summary of the Invention The present invention is directed to a foam forming aerosol cleaning composition that is particularly suited for cleaning hard surfaces. The invention is based in part on the discovery mat the aerosol formulations of a hard-surface cleaner mat includes a chelating agent comprising potassium EDTA and/or ammonium EDTA are superior in applying the cleaner over a surface area without adversely affecting the cleaning abilities of the cleaner.
In one aspect, the invention is directed to a dispensable composition for cleaning hard surfaces that includes:
(a) an anionic, nonionic, amphoteric surfactant, and mixtures thereof with optionally, a quaternary ammonium surfactant, the total amount of said surfactant being present in a cleaning effective amount:
(b) at least one water-soluble or dispersible organic solvent having a vapor pressure of at least 0.001 mm Hg at 25 'C, said at least one organic solvent present in a solubilizing - or dispersion - effective amount;
(c) a chelating agent selected from me group consisting of tetrapotassium ethylenediamine - tetraacetate (potassium EDTA), tetraammonium ethylenediamine-tetraacetate (ammonium EDTA) and mixtures thereof, said chelating agent present in an amount effective to enhance soil removal in said composition;
(d) an effective amount of a propellant; and
(e) die remainder, water. In another aspect, the invention is directed to a device, for dispensing a composition for cleaning hard surfaces, which includes, a closed container containing the above referenced cleaning composition and nozzle means for releasing said composition towards a soiled surface.
Detailed Description of Preferred Embodiments The invention provides an aerosol formulation comprising an improved, all purpose cleaner especially adapted for the complete and speedy removal of soap scum and other bathroom soils from a hard surface. The cleaner is intended to clean hard surfaces by aerosol application of a metered discrete amount of me cleaner by a dispenser onto me surface to be cleaned and then wiping the surface, thus removing the soil and die cleaner, wim or without the need for rinsing with water. Foaming action facilitates dispersal of the active components. The typical bathroom surface is a shower stall, both the glass doors, as well as me vertical wall surfaces (typically made of tile, or composite materials), sinks and glass.
The aerosol formulation comprises a cleaning composition mat is mixed wim a propellant. The cleaning composition or cleaner itself prior to being mixed wim me propellant is preferably a single phase, clear, isotropic solution, having a viscosity generally less than about 100 Centipoise ("cps"). The cleaning composition itself has the following ingredients:
(a) an anionic, nonionic or amphoteric surfactant, and mixtures thereof wim optionally, a quaternary ammonium surfactant, said surfactants being present in a cleaning - effective amount; (b) at least one water-soluble or dispersible organic solvent having a vapor pressure of at least 0.001 mm Hg at 25 'C, said at least one organic solvent present in a solubilizing - or dispersion - effective amount;
(c) a chelating agent selected from ammonium ethylenediamine - tetraaecetate (ammonia EDTA), tetrapotassium emylenediamine - tetraacetate (potassium EDTA), or mixtures thereof, said chelating agent present in an amount effective to enhance soil, especially soap scum, removal in said cleaner; and (d) die remainder, water.
Additional adjuncts in small amounts such as buffers, fragrance, dye and die like can be included to provide desirable attributes of such adjuncts.
In d e application, effective amounts are generally tiiose amounts listed as me ranges or levels of ingredients in me descriptions which follow hereto. Unless otherwise stated, amounts listed in percentage (" %'s") are in weight percent (based on 100% active) of die cleaning composition. 1. Solvents
The solvent is a water soluble or dispersible organic solvent having a vapor pressure of at least 0.001 mm Hg at 25 "C. It is preferably selected from C^ alkanol, C^ diols, C3-24 aikylene glycoi ethers, and mLxmres thereof. The alkanol can be selected from methanol, ethanol, n-propanol. isopropanol. butanol, pentanoi, hexanoi, dieir various positional isomers, and mLxmres of d e foregoing. It may also be possible to utilize in addition to, or in place of, said alkanols, the diols such as memylene, ethylene, propylene and butylene glycols, and mixtures thereof.
It is preferred to use an aikylene glycoi etfier solvent in this invention. The aikylene glycoi ether solvents can include emylene glycoi monobutyl ether, emylene glycoi monopropyl edier, propylene glycoi n-propyl etfier, propylene glycoi monobutyl ether, diemylene glycoi n-butyl ether, dipropylene glycoi memyl ether, and mLxmres mereof. Preferred glycoi ediers are emylene glycoi monobutyl ether, also known as butoxyedianol, sold as butyl Cellosolve by Union Carbide, and also sold by Dow Chemical Co., 2-(2-butoxyethoxy) ethanol, sold as butyl Carbitol, also by Union Carbide, and propylene glycoi n-propyl ether, available from a variety of sources. Anodier preferred aikylene glycoi ether is propylene glycoi, t-butyl ether, which is commercially sold as Arcosolve PTB, by Arco Chemical Co. The n-butyl edier of propylene glycoi is also preferred. Odier suppliers of preferred solvents include Union Carbide. If mLxmres of solvents are used, d e amounts and ratios of such solvents used are important to determine the optimum cleaning and streak/film performances of the inventive cleaner. It is preferred co limit the total amount of solvent to no more than 50% , more preferably no more man 25 , and most preferably, no more man 15 % . of the cleaner. A preferred range is about 1-15 % . These amounts of solvents are generally referred to as dispersion-effective or solubilizing effective amounts, since the other components, such as surfactants. are materials which are assisted into solution by the solvents. The solvents are also important as clearing materials en their own. helping to lcosen and solubilize greasy soils for easy removal from the surface cleaned. 2. Surfactants
The surfactant is an anicnic, nonionic. amphcteric surfactant, or mLxmres thereof. Optionally, a quaternary ammonium surfactant can be added. a. Anionic. Nonionic and Amnhoteric Surfactants
The anionic surfactant is, for example, a linear or branched C_.;4 alkylbenzene sulfonate, alkane sulfoπate. alkyl sulfate. or generally, a sulfated or sulfonated .,4 surfactant. Witconate NAS, for example, is a 1-octane-sulfonate. from Witco Chemical Company. Pilot L-45. a C1! 5 alkylbenzene sulfonate (which are referred to as "LAS"), from Pilot Chemical Co. , Biosoft S100 and S130 (non-neutralized linear alkylbenzene sulfonic acid, which is referred to as "HLAS") and S40 from Stepan Company; sodium dodecyl sulfate and sodium lauryl sulfate. The use of acidic surfactants having a higher actives level may be desirable due to cost-effectiveness.
The nonionic surfactants are selected from alkoxvlated alcohols, alkoxylated phenol ethers, and odier surfactants often referred to as semi-polar nonionics, such as the trialkyl amine oxides. The alkoxylated phenol ethers include octyl- and nonylphenol ediers, with varying degrees of alkoxylation, such as 1-10 moles of ethylene oxide per mole of phenol. The alkyl group can vary from C_.lfi, although octyl- and nonyl chain lengths are readily available. Various suitable products available from Rohm and Haas under the trademark Triton, such as Triton N-57, N-101, N-lll, X-45, X-100, X-102, and from Mazer Chemicals under the trademark Macol, from GAF Corporation under d e trademark Igepal. from Texaco Chemical Company under the trademark Surfonic. Tne alkoxylated alcohols include ethoxylated. and ethoxylated and propoxylated C_.;6 alcohols, with about 2-10 moles of ethylene oxide, or 1-10 and 1-10 moles of ethylene and propylene oxide per mole of alcohol, respectively. Exemplary surfactants are available from Shell Chemical under the trademarks Neodol and Alfonic and Huntsman. The semi-polar amine oxides are aiso preferred, although, for the invention, a mixture of nonionic and amine oxide surfactants can also be used. The amine oxides, referred to as mono-long chain, di-short chain, trialkyl amine oxides, have ±e general configuration:
R2
R'-NO
R3
wherein R1 is C^., alkyl, and R: and R3 are both C14 alkyl, or C hydroxyalkyl, altfiough R: and R3 do not have to be equal. These amine oxides can also be ethoxylated or propoxylated. The preferred amine oxide is lauryl amine oxide. The commercial sources for such amine oxides are Barlox 10, 12, 14 and 16 from Lonza Chemical Company. Varox by Witco and Ammonyx by Stepan Co. A further preferred semi-polar nonionic surfactant is alkylamidoall ylenedialkylamine oxide. Its structure is shown below:
O R2
I
R1 -C-NH-(CH, VNO
I R3
O
wherein R1 is C5.:o alkyl, R- and R3 are C alkyl, R1 -C-NH-(CH^n- or -(CH --OH. although R: and R3 do not have to be equal or d e same substituent. and n is 1-5. preferably 3. and p is i-ό. preferably 2-3. Additionally, the surfactant could be ethoxylated (1-10 moles of EO/mole) or propoxylated (1-10 moles of PO/mole). This surfactant is available from various sources, including from Lonza Chemical Company, as a cccoamidopropyldimethyl amine oxide, sold under the brand name Bariox C. Additionally semi-polar surfactants include phcsphine oxides and sulfoxides.
The amphoteric surfactant is typically an alk lbetaine or a sulfobetaine. One group of preferred amphoterics are alkyiamidoaikyidialkylbetaines. Tnese have the structure:
R:
R1-C-NH-(CH2)m-N^-(CH2)nCOO-
O R3
wherein R1 is C_. o alkyl, R: and R3 are bom C alkyl. although R: and R3 do not have to be equal, and m can be 1-5, preferably 3, and n can be 1-5, preferably 1. These alkvlbetaines can also be ethoxylated or propoxylated. The preferred alkylbetaine is a cocoamidopropyldimethyl betaine called Lonzaine CO, available from Lonza Chemical Co. Other vendors are Henkel KGaA, which provides Velvetex AB, and Witco Chemical Co. , which offers Rewoteric AMB-15, borJa of which products are cocobetaines.
The amounts of surfactants present are to be somewhat minimized, for purposes of cost-savings and to generally restrict the dissolved actives which could contribute to leaving behind residues when die aerosol is applied to a surface. However, die amounts added are generallv about 0.001-10% , more preferably 0.002-3.00% surfactant. These are generally considered to be cleaning-effective amounts. If a mixture of anionic and nonionic or amphoteric surfactants is used, die ratio of the anionic surfactant to the nonionic or amphoteric suπactant is about 20:1 to 1:20. more preferably about 10: 1 to 1: 10. b. Quaternary .Ammonium Surfactant
The invention may further optionally include a cationic surfactant, specifically, a quaternary ammonium surfactant. These types of surfactants are typically used in bathroom cleaners because they are generally considered
"broad spectrum" antimicrobial compounds, having efficacy against bo gram positive (e.g. , S tap hv loco ecus s_ .) and gram negative (e.g.. Escherischia coif* microorganisms. Tnus, the quaternary ammonium surfactant, or compounds. are incorporated for bacteriostatic/disinfectant purposes and should be present in amounts effective for such purposes.
The quaternary ammonium compounds are selected from mono-long-chain, tri-short-chain, tetraalkyl ammonium compounds, di-long-chain. di-short-chain tetraalkyl ammonium compounds, trialkyl, mono-benzyl ammonium compounds, and mLxmres thereof. By "long" chain is meant about
Figure imgf000011_0001
alkyl. By "short" chain is meant C1-3 alkyl, preferably CI-3 . Preferred materials include Stepan series, such as d e BTC 2125 series which comprises di-C_4 tetraalkyl ammonium chloride, Barquat and Bardac series, such as Bardac MB 2050, from Lonza Chemical. Typical amounts of die quaternary ammonium compound range from preferably about 0-5 % , more preferably about 0.001-2%. 3. Chelating Agent
The chelating agent comprises tetraammonium ethylenediamine tetraacetate (referred to as "ammonium EDTA"), tetrapotassium ethylene diaminetetraacetate (referred to as "potassium EDTA"), or mLxmres thereof. The chelating agent is a critical part of die invention. Its use, in place of the standard chelating agent, tetrasodium EDTA, results in not only a surprisingly complete removal of various soils, including badiroom soap scum soils, but an unexpectedly rapid removal as well. The fact that die potassium or ammonium salt of EDTA is so effective versus the tetrasodium salt was quite unawaitea since, in other literature, the potassium and ammonium saits have not been demonstrated to be superior performers as compared to die tetrasodium sait. Potassium EDTA has an advantage over ammonium EDTA in that the former has low or no occr.
The potassium EDTA can favorably be prepared by taking the acid form of EDTA and neutralizing it with KOH in a stoichiometric quantity. For example, to 50g of the acid form of EDTA and 47g deionizεd water, 76g of KOH solution (45 %) can be siowly added, resulting in a 46% K»EDTA solution. The acid form of EDTA can be obtained from Hampshire Chemicals and Aldrich Chemicals. In me neutralization of the acid form of EDTA, it is preferred to use an excess of alkali. Thus, for example, the level of KOH can vary from a stoichiometric quantity to from about a 0 to 5 % excess.
The amount of ammonium EDTA and or potassium EDTA added should be in the range of 0.01-25 %, more preferably 0.01-10% , by weight of the cleaner. Moreover, a discrete quantity of a co-chelant, such as tetrasodium EDTA may be added, in an amount ranging from about 1-5% . 4. Water and Miscellaneous
Since die cleaner is an aqueous cleaner with relatively low levels of actives, die principal ingredient is water, which should be present at a level of at least about 50% , more preferably at least about 80%, and most preferably, at least about 90%. Deionized water is preferred.
Small amounts of adjuncts can be added for improving cleaning performance or aesthetic qualities of the cleaner. For example, buffers could be added to maintain constant pH (which for the invention is between about 7-14, more preferably between about 8-13). These buffers include NaOH. KOH. Na:C03, K;C03, as alkaline buffers, and phosphoric, hydrochloric. sulfuric acids as acidic buffers, and others. KOH is a prererred buffer since, in die invention, one way of obtaining potassium EDTA is to take the acidic EDTA acid and neutralize :: w.± an appropriate, st.ichiometric amount of KOH. Builders, such as phosphates, silicates, and again, carbonates, may be desirable. Further soiu iiizing materials, such as hydrctropes, e.g.. cumene. toluene and xylene sulfonates. may also be desirable. Adjuncts for cleaning include additional surfactants, such as those described in Kirk-Othmer. Encyclopedia of Chemical Technology, 3rd Ed.. Volume 22, pp. 332-432 (Marcel-Dekker, 1983), and McCutcheon's Soaps and Detergents (N. Arner. 1984), which are incorporated herein by reference. Aesthetic adjuncts include fragrances, such as diose available from Givaudan, IFF, Quest, Sozio, Firmenich, Dragoco and others, and dyes and pigments which can be solubilizεd or suspended in the formulation, such as diaminoandiraquinones. Water-insoluble solvents may sometimes be desirable as added grease or oily soil cutting agents. These types of solvents include tertiary alcohols. hydrocarbons (alkanes), pine-oil. d-limonene and od er terpenes and terpene derivatives, and benzyl alcohols. Thickeners, such as calcium carbonate, sodium bicarbonate, aluminum oxide, and polymers, such as poly aery late, starch, xanthan gum, alginates, guar gum, cellulose, and die like, may be desired additives. The use of some of these thickeners (CaCO3 or NaHCO3) is to be distinguished from their potential use as builders, generally by particle size or amount used. 5. Propellant
The cleaning composition is delivered in die form of an aerosol. Specifically, in order to apply and build the foam, die cleaning composition is delivered via a gaseous propellant. The propellant comprises, for example, a hydrocarbon, of from 1 to 10 carbon atoms, such as methane, ediane. n- propane, n-butane. isobutane, n-pentane. isopentane. and mLxmres diereof. The propellant may also be selected form halogenated hydrocarbons including, for example, fluorocarbons. chlorocarbons. chlorofluorccarbons. and mLxmres thereof. Examples of odier suitable propeilants are founded in P. A. Sanders Handbook of Aerosol Technology: (Van Nostrand Reinhold Co.)(l9""9) 2nd Ed. , Pgs. 348-353 and 364-367, which are incorporated herein.
A liquified gas propellant mLxrure comprising about S5% isobutane and 15% propane is preferred because it provides sufficient pressure to expel the cleaning composition from the container and provides good control over the nature of the spray upon discharge of d e aerosol formulation. Preferably, the propeilants comprises about 3 % to 30%, more preferably about 3 % to 8% , and most preferably about 3 % to 6% of d e aerosol formulation.
The aerosol formulation is preferably stored in and dispensed from a pressurized can that is equipped with a nozzle so that an aerosol of die formulation can be readily sprayed onto a surface to create a relatively uniform layer of foam. A preferred nozzle is a toggle valve model ST-76 with an orifice size of 0.016 in. (0.4 mm) that is manufactured by Seaquist Perfect Dispensing, Cary, Illinois. Dispensers are known in the art and are described, for example, in U.S. Patents 4,780,100, 4,652,389, and 3,541,581 which are incorporated herein. Although pressure within die dispenser, i.e., can pressure, does not appear to be critical, a preferred range is about 40 to 58 lbs./hr, more preferably 40 to 50 lbs Jin2, and most preferably 40 to 47 lbs Jin2 at 70° F (21 °C). The corrosion inhibitor is used to prevent or at least reduce die rate of corrosion of a metallic dispenser. Quaternary ammonium surfactants, if present, can cause corrosion. Preferred corrosion inhibitors include, for example: amine neutralized alkyl acid phosphates, amine neutralized alkyl acid phosphates and nitroalkanes. amine neutralized alkyl acid phosphates and volatile amines, diethanoiamides and nitroalkanes. amine carboxylates and nitroalkanes. esters, volatile silicones, amines and mLxmres diereof. Specific inhibitors include, for example, sodium lauryl sarcosinate. sodium meta silicate, sodium benzoate. triethanoiamine. and morphoiine. To provide additional protection, d e interior of die dispenser in contact with the cleaning composition can be coated wi an epoxy phenolic coating. Wnen employed, the corrosion inhibitor preferably comprises about 0.1 % to 1 % . more preferably about 0.1 % to 0.8 % . and most preferably about 0.35 % of die aerosol formulation. Preferably, with addition of the corrosion inhibitor, the pH of the aerosol formulation is greater than 9.5. In loading die dispenser, die non-propellant components of die aerosol formulation are mixed into a concentrate and loaded into the dispenser first. Thereafter, the liquefied gaseous propellant is inserted before die dispenser was fined with a nozzle.
EXPERIMENTAL In die following experiments, inventive aerosol formulations were compared with two commercial bathroom aerosol cleaners, namely. Dow Bathroom Cleaner (Dow Brands) and Lysol Basin Tub & Tile Cleaner (Reckitt & Colman). Table 1 sets forth the non-propellant active components (including corrosium inhibitor) of the two inventive cleaning compositions, one employing potassium EDTA as the chelating agent and die odier employing ammonium EDTA.
TABLE 1
Figure imgf000016_0001
' uty Carbitol (Dow)
2 Butyl Cellosolve (Dow)
3 Barlox 12 (Lonza)
4 Stepan BTC 2125M (Lonza) 5 Marprosyl 30 (Stephan)
6 Diproproylene glycoi ether added for VOC compliance.
Preparation of Bathroom Soil (Protocol D A laboratory soil (CSMA No. D-5343-93) combining sebum, dirt and soap scum precipitate was prepared. This is a mixture of potting soil, synthetic sebum (mixture of saturated and unsaturated long chain fatty acids, paraffin, cholesterol and sperm wax, among other materials) and stearate premix (calcium stearate, magnesium stearate and iron stearate). The laboratory soil was applied to pre-bakεd white tiles and dried in an oven at 75-80 'C for one hour.
Preparation of Simulated Aged Soap Scum (Protocol IT)
This laboratory soil (modified from Industry accepted standards) simulates aged soap scum and was prepared by making a calcium stearate suspension (ethanol. calcium stearate and water). This soap scum soil was men sprayed onto black ceramic tiles which were baked at 165 ' -170 " C for one hour, then cooled.
Example 1 One Coat Soap Scum
This example employed tiles prepared by die method described in Protocol π to which 2 grams of the aerosol compositions were applied to each tile. After the foam had dissipated, which typically occurred in about 45 seconds, die tile was wiped wid a sponge. The tile was visually graded by a panel of expert graders on a 1 to 10 scale, where 1 indicates no soil removal, while 10 indicates complete removal. The observed results are averaged and subject to error analysis using Fisher's least significant difference ("LSD"), wiu a confidence level of 95%. The results are set form in Table 2. As is apparent, the inventive aerosol formulations were superior to die comparative aerosol cleansers.
Example 2 Bathroom Soil Removal Test In this example, a proprietary and automated reader/scrubber was utilized. The reader/scrubber measures % soil removal by calibrating with a clean tile, which would establish 100% clean, versus a completely soiled tile, which would establish a zero % clean. Each soiled tile cleaned by the scrubber is measured during die cleaning by die reader to establish the differences in shading between die initially completely soiled panel and die completely cleaned one. The number of cycles to remove 90% of die badiroom soil were measured. Tiles coated with bathroom soil (Protocol I) were used. 15 grams of me aerosol compositions were applied to a previously wetted sponge on die scrubber. The results are depicted in Table 2. These scores are again within die 95% confidence level. The inventive aerosol formulations clearly and unambiguously outperformed the aerosol commercial cleaners.
Example 3 Soap Scum Removal Test
In this example, dies prepared by Protocol II were each coated with 15 grams of an aerosol composition and men tested with the reader/scrubber described in Example 2. The number of cycles to remove 90% of die soap scum were measured. The results are depicted in Table 2. These scores are again within the 95% confidence level. The inventive aerosol formulations again clearly and unambiguously outperformed die commercial aerosol cleaners. TABLE 2
Figure imgf000019_0001
The foregoing has described the principles, preferred embodiments and modes of operation of the present invention. However, the invention should net be construed as being limited to die particular embodiments discussed. Thus, the above-described embodiments should be regarded as illustrative rather dian restrictive, and it should be appreciated diat variations may be made in tfiose embodiments by workers skilled in die art without departing from die scope of the present invention as defined by the following claims.

Claims

What Is Claimed Is:
1. A dispensable composition for hard surface cleaning with improved soil removal comprising:
(a) an anionic, nonionic, amphoteric surfactant, and mixtures thereof with optionally, a quaternary ammonium' surfactant, die total amount of said surfactant being present in a cleaning effective amount;
(b) at least one water-soluble or dispersible organic solvent having a vapor pressure of at least 0.001 mm Hg at 25 *C, said at least one organic solvent present in a solubilizing - or dispersion - effective amount; (c) a chelating agent selected from the group consisting of tetrapotassium ethylenediamine - tetraacetate (potassium EDTA), tetraammonium ethylenediamine-tetraacetate (ammonium EDTA) and mLxmres thereof, said chelating agent present in an amount effective to enhance soil removal in said composition; (d) an effective amount of a propellant; and
(e) die remainder, water.
2. The composition of Claim 1 wherein the chelating agent comprises potassium EDTA.
3. The composition of Claim 1 wherein said surfactant is an anionic surfactant of (a), which further comprises a linear or branched
Figure imgf000020_0001
alkylbenzene sulfonate, alkane sulfonate, alkyl sulfate, and mLxmres thereof.
4. The composition of Claim 1 wherein said surfactant of (a) is a nonionic surfactant, which further comprises an alkoxylated alkylphenol edier, an alkoxylated alcohol, or a semi-polar nonionic surfactant.
5. The composition of Claim 4 wherein said nonionic surfactant is a semi-polar nonionic surfactant selected from me group consisting of mono-long-chain alkyl, di-short-chain trialkyl amine oxides, alkylamidodialkyl amine oxides, phosphine oxides and sulfoxides.
6. The composition of Claim 5 wherein said nonionic surfactant of (a) is a mono-long-chain, di-short-chain trialkyl amine oxide.
7. The composition of Claim 4 wherein said nonionic surfactant is an ethoxylated alkylphenol ether selected from me group consisting of edioxylated octylphenol ediers, ethoxylated nonylphenol ediers, and mLxmres thereof.
8. The composition of Claim 7 wherein said nonionic surfactant is an ethoxylated octylphenol, edioxylated wim 1-10 moies of ethylene oxide.
9. The composition of Claim 1 wherein said organic solvent of (b) is selected from the group consisting of alkanols, diols, glycoi ediers, and mixtures thereof.
10. The composition of Claim 9 wherein said organic solvent is a C3._4 glycoi edier.
11. The composition of Claim 1 further comprising a quaternary ammonium compound.
12. The composition of Claim 11 wherein said quaternary ammonium compound is selected from me group consisting of mono-long-chain, tri-short-chain, tetraalkyl ammonium compounds, di-long-chain, di-short-chain tetra-alkyl ammonium compounds, trialkyl, mono-benzyl ammonium compounds, and mixtures thereof.
13. The composition of claim 1 further comprising at least one adjunct selected from die group consisting of builders, buffers, fragrances, thickeners, dyes, pigments, foaming stabilizers, water-insoluble organic solvents, and hydrotropes.
14. The composition of claim 1 wherein said tetrapotassium EDTA is prepared by neutralizing die acid form of EDTA.
15. The composition of claim 14 wherein the neutralizing agent is potassium hydroxide.
16. The composition of claim 15 wherein said potassium hydroxide is present in a stoichiometric to slighdy greater than stoichiometric amount.
17. The composition of claim 1 further comprising tetrasodium EDTA as a co-chelant.
18. A method for removing a soil from a hard surface, said metiiod comprising the steps of:
(i) forming a foam by delivering an admixture via a propellant, wherein me admixture and propellant are derived from a composition comprising: (a) either an anionic, nonionic, amphoteric surfactant, and mixtures thereof with optionally, a quaternary ammonium surfactant, die total amount of said surfactant being present in a cleaning effective amount; (b) at least one water-soluble or dispersible organic solvent having a vapor pressure of at least 0.001 mm Hg at 25 *C, said at least one organic solvent present in a solubilizing or dispersion - effective amount;
(c) a chelating agent selected from die group consisting of tetrapotassium emylenediamine - tetraacetate (potassium EDTA) tetraammonium e ylene-ammonium-tetraacetate (ammonium EDTA), and mixtures thereof said chelating agent present in an amount effective to enhance soil removal in said composition;
(d) an effective amount of a propellant; and (e) the remainder, water; and
(ii) applying said foam to a soiled hard surface.
19. The method of Claim 18 further comprising removing said soil and said admixture from said surface.
20. The method of Claim 18 wherein die chelating is potassium EDTA.
21. A device for dispensing a composition for cleaning soil from a hard surface which comprises:
(i) a closed container containing said composition which comprises: (a) eitiier an anionic, nonionic, amphoteric surfactant, and mixtures diereof with optionally, a quaternary ammomum surfactant, the total amount of said surfactant being present in a cleaning effective amount; (b) at least one water-soluble or dispersible organic solvent having a vapor pressure of at least 0.001 mm Hg at 25 "C, said at least one organic solvent present in a solubilizing or dispersion - effective amount; (c) a chelating agent selected from the group consisting of tetrapotassium eύhylenediamine - tetraacetate (potassium EDTA) tetraammonium ethylene-ammonium-tetraacetate (ammomum EDTA), and mixtures thereof said chelating agent present in an amount effective to enhance soil removal in said composition;
(d) an effective amount of a propellant;
(e) me remainder, water; and
(ϋ) nozzle means for releasing said composition towards die hard surface whereupon non-propellant components admix and interact witia said propellant to form a foam on said surface.
PCT/US1998/005224 1997-03-28 1998-03-16 Aerosol hard surface cleaner with enhanced soil removal WO1998044080A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CA002291223A CA2291223A1 (en) 1997-03-28 1998-03-16 Aerosol hard surface cleaner with enhanced soil removal
EP98910456A EP1015535A1 (en) 1997-03-28 1998-03-16 Aerosol hard surface cleaner with enhanced soil removal
AU64695/98A AU760853B2 (en) 1997-03-28 1998-03-16 Aerosol hard surface cleaner with enhanced soil removal

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/827,546 1997-03-28
US08/827,546 US5948741A (en) 1996-04-12 1997-03-28 Aerosol hard surface cleaner with enhanced soil removal

Publications (1)

Publication Number Publication Date
WO1998044080A1 true WO1998044080A1 (en) 1998-10-08

Family

ID=25249493

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1998/005224 WO1998044080A1 (en) 1997-03-28 1998-03-16 Aerosol hard surface cleaner with enhanced soil removal

Country Status (6)

Country Link
US (1) US5948741A (en)
EP (1) EP1015535A1 (en)
AR (1) AR012200A1 (en)
AU (1) AU760853B2 (en)
CA (1) CA2291223A1 (en)
WO (1) WO1998044080A1 (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999043773A1 (en) * 1998-02-26 1999-09-02 Reckitt & Colman Products Limited Improvements in or relating to organic compositions
WO2000071662A1 (en) * 1999-05-21 2000-11-30 Reckitt Benckiser Inc. Low residue aqueous hard surface cleaning and disinfecting compositions
WO2001068793A1 (en) * 2000-03-15 2001-09-20 Henkel Kommanditgesellschaft Auf Aktien Cleaning agent
WO2002097018A1 (en) * 2001-05-30 2002-12-05 Reckitt Benckiser Inc Foam alkaline hard surface cleaner
WO2005118765A1 (en) * 2004-05-24 2005-12-15 Ecolab Inc. Foam cleaning composition, method for foaming a cleaning composition, and foam dispenser
DE102005051866A1 (en) * 2005-10-25 2007-05-03 Beiersdorf Ag Use of 1,2-alkanediols for improving the foaming behavior of gel-like, polyacrylate-thickened cleaning preparations
WO2007082685A1 (en) * 2006-01-23 2007-07-26 Henkel Kommanditgesellschaft Auf Aktien Sprayable all-purpose cleaner
US7964544B2 (en) 2005-10-31 2011-06-21 Ecolab Usa Inc. Cleaning composition and method for preparing a cleaning composition

Families Citing this family (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5972876A (en) 1996-10-17 1999-10-26 Robbins; Michael H. Low odor, hard surface cleaner with enhanced soil removal
US6245728B1 (en) 1996-10-17 2001-06-12 The Clorox Company Low odor, hard surface cleaner with enhanced soil removal
US6090771A (en) * 1996-10-24 2000-07-18 Reckitt Benckiser Inc. Low residue aqueous hard surface cleaning and disinfecting compositions
US6159916A (en) * 1998-06-12 2000-12-12 The Clorox Company Shower rinsing composition
US6153571A (en) * 1999-01-29 2000-11-28 Sports Care Products, Inc. Terpene based aqueous cleaning gel for sporting equipment
US6425406B1 (en) * 1999-09-14 2002-07-30 S. C. Johnson & Son, Inc. Toilet bowl cleaning method
WO2001025379A1 (en) * 1999-10-04 2001-04-12 The Procter & Gamble Company Fluid cleaning compositions having high levels of amine oxide
US6350727B1 (en) 2000-01-28 2002-02-26 Amway Corporation Non-streaking no-wipe cleaning compositions with improved cleaning capability
US6316398B1 (en) * 2000-05-09 2001-11-13 Diversey Lever, Inc. General purpose cleaning composition
AUPQ893200A0 (en) * 2000-07-21 2000-08-17 Whiteley, Reginald K. Medical residue treatment
MXPA03002213A (en) * 2000-09-14 2003-06-24 Stepan Co Antimicrobial ternary surfactant blend comprising cationic, anionic, and bridging surfactants, and methods of preparing same.
GB2370042A (en) * 2000-12-15 2002-06-19 Reckitt Benckiser Inc Hard surface cleaning compositions
JP3805629B2 (en) * 2001-02-15 2006-08-02 花王株式会社 Liquid bleach detergent composition
US20050239675A1 (en) * 2002-04-01 2005-10-27 Munzer Makansi Carrier foam to enhance liquid functional performance
US20050008576A1 (en) * 2002-04-01 2005-01-13 Munzer Makansi Carrier foam to enhance liquid functional performance
GB2391234A (en) * 2002-07-24 2004-02-04 Reckitt Benckiser Inc Hard surface cleaning compositions
US20040120915A1 (en) * 2002-12-19 2004-06-24 Kaiyuan Yang Multifunctional compositions for surface applications
US6868989B2 (en) * 2003-03-10 2005-03-22 S.C. Johnson & Son, Inc. Cleaner with adjustable aerosol canister retainer
US20040254085A1 (en) * 2003-05-19 2004-12-16 Johnsondiversey, Inc. [high caustic contact cleaner]
US20050227898A1 (en) * 2004-04-09 2005-10-13 Leskowicz James J Zero to low VOC glass and general purpose cleaner
US6969698B2 (en) * 2004-04-13 2005-11-29 S. C. Johnson & Son, Inc. Aerosol cleaner
EP1734106A1 (en) * 2005-06-14 2006-12-20 Reckitt Benckiser (UK) LIMITED Cleaning composition and method
US8034756B2 (en) * 2006-04-21 2011-10-11 Dow Global Technologies Llc Formulations with unexpected cleaning performance incorporating a biodegradable chelant
US7691800B2 (en) * 2006-08-30 2010-04-06 B-Tech Ip Holdings, Llc Water-based cleaning agent and method for cleaning a spray gun
US8143205B2 (en) 2008-02-21 2012-03-27 S.C. Johnson & Son, Inc. Cleaning composition having high self-adhesion and providing residual benefits
US8980813B2 (en) 2008-02-21 2015-03-17 S. C. Johnson & Son, Inc. Cleaning composition having high self-adhesion on a vertical hard surface and providing residual benefits
US8143206B2 (en) 2008-02-21 2012-03-27 S.C. Johnson & Son, Inc. Cleaning composition having high self-adhesion and providing residual benefits
US9481854B2 (en) 2008-02-21 2016-11-01 S. C. Johnson & Son, Inc. Cleaning composition that provides residual benefits
US9410111B2 (en) 2008-02-21 2016-08-09 S.C. Johnson & Son, Inc. Cleaning composition that provides residual benefits
US8993502B2 (en) 2008-02-21 2015-03-31 S. C. Johnson & Son, Inc. Cleaning composition having high self-adhesion to a vertical hard surface and providing residual benefits
CN103179855B (en) * 2010-06-30 2015-07-08 刘慧文 Antimicrobial complexes
US8455551B2 (en) 2011-03-04 2013-06-04 American Sterilizer Company Broad spectrum disinfectant
EP2985331B1 (en) * 2011-09-21 2019-08-21 Ecolab USA Inc. Development of extensional viscosity for reduced atomization for diluted concentrate sprayer applications
GB201211691D0 (en) 2012-07-05 2012-08-15 Reckitt Benckiser Llc Sprayable aqueous alcoholic microbicidal compositions comprising zinc ions
GB201211702D0 (en) 2012-07-02 2012-08-15 Reckitt Benckiser Llc Sprayable aqueous alcoholic microbicidal compostions comprising zinc ions
GB201211688D0 (en) 2012-07-02 2012-08-15 Reckitt Benckiser Llc Aqueous alcoholic microbicidal compositions comprising zinc ions
GB201211701D0 (en) 2012-07-02 2012-08-15 Reckitt Benckiser Llc Aqueous alcoholic microbicidal compositions comprising zinc ions
US8927479B2 (en) * 2012-08-30 2015-01-06 The Clorox Company Aerosol bathroom cleaner
US9707162B2 (en) 2012-11-30 2017-07-18 Reckitt & Colman (Overseas) Limited Microbicidal personal care compositions comprising metal ions
US9757006B2 (en) * 2013-03-26 2017-09-12 The Procter & Gamble Company Articles for cleaning a hard surface
JP6516353B2 (en) * 2014-12-26 2019-05-22 ライオン株式会社 Liquid cleaning agent for bathroom
JP6571867B2 (en) * 2015-07-14 2019-09-04 エコラボ ユーエスエー インコーポレイティド Controlled foam breaking rate in hard surface cleaners
US10000728B2 (en) 2015-07-17 2018-06-19 S. C. Johnson & Son, Inc. Cleaning composition with propellant
CN110997117B (en) 2017-06-30 2023-08-01 戴弗西公司 Membrane cleaning solution and method for accelerating membrane cleaning using the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USH269H (en) * 1985-03-11 1987-05-05 A. E. Staley Manufacturing Company Disinfectant and/or sanitizing cleaner compositions
US4687592A (en) * 1985-02-19 1987-08-18 The Procter & Gamble Company Detergency builder system
US4749516A (en) * 1985-09-24 1988-06-07 S. C. Johnson & Son, Inc. Anionic emulsion pre-spotting composition
US5380454A (en) * 1993-07-09 1995-01-10 Reckitt & Colman Inc. Low temperature non-caustic oven cleaning composition

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4029607A (en) * 1974-03-29 1977-06-14 The Drackett Company Drain cleaning compositions
US4207215A (en) * 1977-12-12 1980-06-10 The Drackett Company Tile and grout cleaner
US4158644A (en) * 1978-03-17 1979-06-19 Kewanee Industries, Inc. Cleaner and grease emulsifier
US4530781A (en) * 1983-10-12 1985-07-23 S. C. Johnson & Son, Inc. Metastable prespotting composition
US4595527A (en) * 1984-09-25 1986-06-17 S. C. Johnson & Son, Inc. Aqueous laundry prespotting composition
US4637899A (en) * 1984-01-30 1987-01-20 Dowell Schlumberger Incorporated Corrosion inhibitors for cleaning solutions
DD228561B1 (en) * 1984-11-13 1987-09-02 Petrolchemisches Kombinat CLEANING AGENTS FOR ENAMELED FLAKES
DE3681378D1 (en) * 1985-08-14 1991-10-17 Pumptech Nv METHOD AND COMPOSITION FOR INHIBITING CORROSION OF IRON AND STEEL.
US4734259A (en) * 1985-11-22 1988-03-29 Dowell Schlumberger Incorporated Mixtures of α,β-unsaturated aldehides and surface active agents used as corrosion inhibitors in aqueous fluids
DE3708938A1 (en) * 1987-03-19 1988-09-29 Henkel Kgaa LIQUID, PHOSPHATE-FREE SINGLE-PHASE DEGREASING AGENT FOR ALUMINUM SURFACES
EP0496433B1 (en) * 1987-10-22 1999-03-24 The Procter & Gamble Company Photoprotection compositions comprising chelating agents
JPH02180999A (en) * 1989-01-05 1990-07-13 Igarashi Takao Neutral cleaner composition for cleaning machine
US5062987A (en) * 1990-10-09 1991-11-05 Basf Corporation Cooling system cleaning solutions
US5071582A (en) * 1990-08-06 1991-12-10 Basf Corporation Coolant system cleaning solutions having silicate or siliconate-based corrosion inhibitors
US5585342A (en) * 1995-03-24 1996-12-17 The Clorox Company Reduced residue hard surface cleaner
US5468423A (en) * 1992-02-07 1995-11-21 The Clorox Company Reduced residue hard surface cleaner
US5252245A (en) * 1992-02-07 1993-10-12 The Clorox Company Reduced residue hard surface cleaner
US5328561A (en) * 1992-07-10 1994-07-12 Macdermid Incorporated Microetchant for copper surfaces and processes for using same
US5266121A (en) * 1992-08-12 1993-11-30 Helion Industries, Inc. Method of cleaning photographic processing equipment
DE69422081T2 (en) * 1993-04-19 2000-07-20 Reckitt & Colman Inc., Wayne General purpose detergent composition
US5417887A (en) * 1993-05-18 1995-05-23 The Dow Chemical Company Reduced viscosity, organic liquid slurries of aluminum nitride powder
US5439901A (en) * 1993-07-23 1995-08-08 The Procter & Gamble Company Cyproterone thiopivalate
US5536452A (en) * 1993-12-07 1996-07-16 Black; Robert H. Aqueous shower rinsing composition and a method for keeping showers clean
US5476615A (en) * 1994-05-20 1995-12-19 Lonza Inc. Low foam sanitizers
US5972876A (en) * 1996-10-17 1999-10-26 Robbins; Michael H. Low odor, hard surface cleaner with enhanced soil removal
US5814591A (en) * 1996-04-12 1998-09-29 The Clorox Company Hard surface cleaner with enhanced soil removal

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4687592A (en) * 1985-02-19 1987-08-18 The Procter & Gamble Company Detergency builder system
USH269H (en) * 1985-03-11 1987-05-05 A. E. Staley Manufacturing Company Disinfectant and/or sanitizing cleaner compositions
US4749516A (en) * 1985-09-24 1988-06-07 S. C. Johnson & Son, Inc. Anionic emulsion pre-spotting composition
US5380454A (en) * 1993-07-09 1995-01-10 Reckitt & Colman Inc. Low temperature non-caustic oven cleaning composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1015535A4 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999043773A1 (en) * 1998-02-26 1999-09-02 Reckitt & Colman Products Limited Improvements in or relating to organic compositions
US6358900B1 (en) 1998-02-26 2002-03-19 Reckitt Benckiser (Uk) Limited Hard surface cleaners comprising an ethoxylated quaternary ammonium compound and an anionic surfactant
WO2000071662A1 (en) * 1999-05-21 2000-11-30 Reckitt Benckiser Inc. Low residue aqueous hard surface cleaning and disinfecting compositions
US6667289B2 (en) 1999-05-21 2003-12-23 Reckitt Benckiser Inc. Low residue aqueous hard surface cleaning and disinfecting compositions
WO2001068793A1 (en) * 2000-03-15 2001-09-20 Henkel Kommanditgesellschaft Auf Aktien Cleaning agent
WO2002097018A1 (en) * 2001-05-30 2002-12-05 Reckitt Benckiser Inc Foam alkaline hard surface cleaner
US7666826B2 (en) 2002-11-27 2010-02-23 Ecolab Inc. Foam dispenser for use in foaming cleaning composition
US7879785B2 (en) 2002-11-27 2011-02-01 Ecolab Inc. Method for foaming a cleaning composition
WO2005118765A1 (en) * 2004-05-24 2005-12-15 Ecolab Inc. Foam cleaning composition, method for foaming a cleaning composition, and foam dispenser
DE102005051866A1 (en) * 2005-10-25 2007-05-03 Beiersdorf Ag Use of 1,2-alkanediols for improving the foaming behavior of gel-like, polyacrylate-thickened cleaning preparations
US7964544B2 (en) 2005-10-31 2011-06-21 Ecolab Usa Inc. Cleaning composition and method for preparing a cleaning composition
WO2007082685A1 (en) * 2006-01-23 2007-07-26 Henkel Kommanditgesellschaft Auf Aktien Sprayable all-purpose cleaner

Also Published As

Publication number Publication date
EP1015535A4 (en) 2000-07-05
CA2291223A1 (en) 1998-10-08
EP1015535A1 (en) 2000-07-05
US5948741A (en) 1999-09-07
AU6469598A (en) 1998-10-22
AR012200A1 (en) 2000-09-27
AU760853B2 (en) 2003-05-22

Similar Documents

Publication Publication Date Title
US5948741A (en) Aerosol hard surface cleaner with enhanced soil removal
CA2328247C (en) Aerosol hard surface cleaner for removing bathroom soil
US6214784B1 (en) Low odor, hard surface cleaner with enhanced soil removal
US6399555B2 (en) Low odor, hard surface cleaner with enhanced soil removal
US5814591A (en) Hard surface cleaner with enhanced soil removal
CA2884691C (en) Aerosol bathroom cleaner
AU748915C (en) Reduced residue hard surface cleaner
CA2383866A1 (en) Antimicrobial hard surface cleaner
WO2001031110A1 (en) Low odor, hard surface abrasive cleaner with enhanced soil removal
US20040254085A1 (en) [high caustic contact cleaner]
AU2762400A (en) Reduced residue hard surface cleaner

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR CA JP KR PL

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1998910456

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2291223

Country of ref document: CA

Ref country code: CA

Ref document number: 2291223

Kind code of ref document: A

Format of ref document f/p: F

WWE Wipo information: entry into national phase

Ref document number: 64695/98

Country of ref document: AU

NENP Non-entry into the national phase

Ref country code: JP

Ref document number: 1998541681

Format of ref document f/p: F

WWP Wipo information: published in national office

Ref document number: 1998910456

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 64695/98

Country of ref document: AU

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载